Perfume precursor

Abstract

A fragrance precursor represented by formula (1): ##STR00001##
wherein R.sup.1 represents a hydrogen atom, an alkyl group having a carbon number of 1 to 12, a hydroxy group, a methoxy group or an ethoxy group R.sup.2 represents a single bond, an alkylene group having a carbon number of 1 to 2, which may have a substituent, or a vinylene group which may have a substituent; and R.sup.3 represents a residue resulting from removal of one hydrogen atom of a hydroxy group from a fragrance alcohol having a carbon number of 5 to 20 or a phenol which may have a substituent.

Claims

1. A method for releasing a fragrance alcohol, a phenol or a phenol derivative, comprising reacting a fragrance precursor of the following formula (1) with a microorganism in a microbial culture, ##STR00141## wherein R.sup.1 represents a hydrogen atom, an alkyl group having a carbon number of 1 to 12, a hydroxy group, a methoxy group or an ethoxy group; R.sup.2 represents a single bond, an alkylene group having a carbon number of 1 to 2, which may have a substituent, or a vinylene group which may have a substituent; and R.sup.3 represents a residue resulting from removal of one hydrogen atom of a hydroxy group from a fragrance alcohol having a carbon number of 5 to 20 or a phenol which may have a substituent, wherein the microorganism is one or more species selected from the group consisting of Bacillus subtilis and Moraxella osloensis, an amount of the microorganism in the microbial culture is from 10.sup.3 to 10.sup.12 cfu/mL, and a mass of the fragrance precursor at the time of mixing with the microbial culture is from 0.01 to 10 mg per 1 mL of the microbial culture.

Description

DESCRIPTION OF EMBODIMENTS

(1) The present invention is described in detail below.

(2) Note that in the present invention, the “mass” has the same meaning as “weight”.

(3) In the present invention, an alcohol, a phenol or a phenol derivative, which are an aromatic component, can be generated by reacting a fragrance precursor represented by general formula (1) or the later-described compounds 001 to 118 with a hydrolase or microorganism.

(4) [Fragrance Precursor]

(5) The fragrance precursor of the present invention is represented by the following formula (1):

(6) ##STR00003##

(7) In formula (1), R.sup.1 represents a hydrogen atom, an alkyl group having the carbon number of 1 to 12, a hydroxy group, a methoxy group or an ethoxy group.

(8) The alkyl group having the carbon number of 1 to 12 may be linear or branched and includes, for example, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group.

(9) Among these, in view of scent emission performance, R.sup.1 is preferably a hydrogen atom, a hydroxy group or a methoxy group, more preferably a hydrogen atom.

(10) In formula (1), R.sup.2 represents a single bond, an alkylene group having the carbon number of 1 to 2 which may have a substituent, or a vinylene group which may have a substituent.

(11) The alkylene group having the carbon number of 1 to 2 includes a methylene group and an ethylene group.

(12) The substituent that the alkylene group or vinylene group may have includes, for example, a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom), a hydroxy group, an amino group, a mercapto group, an alkyl group having the carbon number of 1 to 8 (e.g., methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-octyl group, 2-ethylhexyl group, cyclohexyl group), an alkenyl group having the carbon number of 2 to 5 (e.g., vinyl group, allyl group, prenyl group, cyclopenten-1-yl group), an alkynyl group having the carbon number of 2 to 3 (e.g., ethynyl group, propargyl group), an aryl group having the carbon number of 6 to 10 (e.g., phenyl group, p-tolyl group, naphthyl group), a heterocyclic group (e.g., 1-pyrazolyl group, 1-imidazolyl group, 2-furyl group, 2-thienyl group, 4-pyrimidinyl group, 2-pyridyl group, 2-benzothiazolyl group), a nitro group, a cyano group, a carbamoyl group, a sulfamoyl group, an acyl group (e.g., formyl group, acetyl group, pivaloyl group, benzoyl group), an alkoxycarbonyl group (e.g., methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyl group, isobutoxycarbonyl group, an aryloxycarbonyl group (e.g., phenoxycarbonyl group, naphthoxycarbonyl group), a heterocyclic oxycarbonyl group (e.g., 1-pyrazolyloxycarbonyl group, 1-imidazolyloxycarbonyl group, 2-furyloxycarbonyl group, 2-thienyloxycarbonyl group, 2-tetrahydrofuryloxycarbonyl group, 2-morpholyloxycarbonyl group), an imido group (e.g., N-succinimido group, N-phthalimido group), an alkylsulfinyl group (e.g., methylsulfinyl group, ethylsulfinyl group), an arylsulfinyl group (e.g., phenylsulfinyl group), an alkylsulfonyl group (e.g., methylsulfonyl group, ethylsulfonyl group, cyclohexylsulfonyl group), an arylsulfonyl group (e.g., phenylsulfonyl group), a heterocyclic sulfonyl group (e.g., 2-tetrahydropyranylsulfonyl group), a phosphino group (e.g., dimethylphosphino group, diphenylphosphino group), and a phosphinyl group (e.g., phosphinyl group, diethoxyphosphinyl group).

(13) Among these, in view of scent emission performance, R.sup.2 is preferably a single bond.

(14) In formula (1), R.sup.3 represents a residue resulting from removal of one hydrogen atom of a hydroxy group from a fragrance alcohol having the carbon number of 5 to 20 or a phenol which may have a substituent.

(15) The fragrance alcohol is described here. In the present description, the fragrance alcohol means a hydroxy group-containing scented compound that is used as a fragrance.

(16) Preferable examples of the fragrance alcohol having the carbon number of 5 to 20 include, specifically, an aliphatic alcohol [for example, isoamyl alcohol, isopulegol, 2-ethylhexanol, 1-octanol, 3-octanol, 1-octen-3-ol, 1-decanol, 1-dodecanol, 2,6-nonadienol, nonanol, 2-nonanol, cis-6-nonenol, trans-2, cis-6-nonadienol, cis-3, cis-6-nonadienol, butanol, hexanol, cis-2-hexenol, cis-3-hexenol, cis-4-hexenol, trans-2-hexenol, trans-3-hexenol, 1-undecanol, heptanol, 2-heptanol, 3-methyl-1-pentanol, 2,6-dimethylheptanol, p-tert-butylcyclohexanol, o-tert-butylcyclohexanol, p-isopropylcyclohexylmethanol, ambrinol, 1-(2,2,6-trimethylcyclohexyl)-3-hexanol, 9-decenol, 4-methyl-3-decen-5-ol, methyltrimethylcyclopentenylbutenol, ethyltrimethylcyclopentenylbutenol, 3-methyl-5-(2,2,3-trimethylcyclopent-3-en-1-yl)-pentan-2-ol, 3,3-dimethyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-4-pentan-2-ol, 3-methyl-5-(2,2,3-trimethyl-3-cyclopenten-1-yl)-penten-2-ol, p-isopropylcyclohexanol, 2,4-dimethyl-3-cyclohexene-1-methanol, 1-(2-tert-butylcyclohexyl)-2-butanol, {1-methyl-2-[(1,2,2-trimethylbicyclo[3.1.0]hex-3-yl)methyl]cyclopropyl}methanol, 1-(4-isopropyl-cyclohexyl)ethanol, 2-{(1,7,7-trimethylbicyclo[2.2.1]-2-heptyl)oxy}-1-ethanol, 4-cyclohexyl-2-methylbutan-2-ol, (1R,2S)-2-pentylcyclopentan-1-ol, etc.], a terpene alcohol [for example, carveol, borneol, isoborneol, piperitol, geraniol, tetrahydrogeraniol, α- or β-fenchyl alcohol, 2-methylfenchyl alcohol, α- or p-santalol, citronellol, 4-thujanol, terpineol, 4-terpineol, dihydroterpineol, nerol, myrcenol, myrtenol, mugol, tetrahydromugol, menthol, dihydromyrcenol, tetrahydromyrcenol, lavandulol, nopol, nerolidol, hydroxycitronerol, farnesol, perilla alcohol, rhodinol, linalool, dihydrolinalool, tetrahydrolinalool, ethyllinalool, isopulegol, dihydrofarnesol, isocamphylcyclohexanol, vetiverol, cedrol, patchouli alcohol, etc.], an aromatic alcohol [for example, anise alcohol, α-amylcinnamic alcohol, 3-methyl-5-phenylpentanol-1, isopropylbenzylcarbinol, carvacrol, cuminic alcohol, dimethylbenzylcarbinol, dimethylphenylethylcarbinol, cinnamic alcohol, phenylallyl alcohol, phenylethylcarbinol, phenylethyl alcohol, 3-phenylpropyl alcohol, benzyl alcohol, 2-methyl-4-phenylpentanol, 2,2-dimethyl-3-(3-methylphenyl)propanol, 3-methyl-5-phenylpentanol-1,2-methyl-5-phenylpentan-1-ol, 4-methyl-2(2-methylpropyl)tetrahydro-2H-4-pyranol, etc.], eugenol, isoeugenol, dihydroeugenol, 2-methoxy-4-vinylphenol, thymol, hinokithiol, guaiacol, chavicol, salicylaldehyde, hydroxycitronellal, hydroxycitronellal dimethyl acetal, hydroxycitronellal diethyl acetal, vanillin propylene glycol acetal, ethylvanillin, vanillin, vanitrope, 4-methyl-2-ethoxyphenol, methyl lavender ketone, furaneol, raspberry ketone, maltol, ethylmaltol, zingerone, methyl salicylate, ethyl salicylate, butyl salicylate, isobutyl salicylate, amyl salicylate, isoamyl salicylate, prenyl salicylate, hexyl salicylate, cis-3-hexenyl salicylate, cyclohexyl salicylate, benzyl salicylate, phenylethyl salicylate, isopropoxyethyl salicylate, ethyl lactate, and methyl atrarate.

(17) The phenol which may have a substituent includes, for example, the following compounds.

(18) ##STR00004##

(19) Among these, in view of aroma, R.sup.3 is preferably a residue resulting from removal of one hydrogen atom of a hydroxy group from a fragrance alcohol having the carbon number of 6 to 15.

Specific Examples of Compound Represented by General Formula (1)

(20) Specific examples of the compound represented by general formula (1) of the present invention include the later-described compounds 001 to 118 and the following compound.

(21) ##STR00005##

(22) In addition, specific examples of the compound represented by general formula (1) of the present invention include the following compounds synthesized in Examples later. In the following compounds, nPr stands for a normal-propyl group and Me stands for a methyl group.

(23) ##STR00006## ##STR00007##

(24) Furthermore, specific examples of the compound represented by general formula (1) of the present invention include geranyl benzoate, geranyl phenylacetate, geranyl salicylate, phenylethyl benzoate, phenylethyl phenylacetate, phenylethyl salicylate, phenylethyl cinnamate, citronellyl benzoate, citronellyl phenylacetate, citronellyl salicylate, linalyl benzoate, linalyl cinnamate, linalyl phenylacetate, linalyl salicylate, cinnamyl benzoate, cinnamyl cinnamate, eugenyl benzoate, eugenyl phenylacetate, eugenyl salicylate, isoeugenyl benzoate, isoeugenyl phenylacetate, isoeugenyl salicylate, menthyl benzoate, menthyl phenylacetate, menthyl salicylate, rhodinyl benzoate, rhodinyl phenylacetate, neryl benzoate, neryl phenylacetate, neryl salicylate, terpinyl benzoate, anisyl benzoate, anisyl phenylacetate, anisyl salicylate, cis-3-hexenyl benzoate, cis-3-hexenyl phenylacetate, cis-3-hexenyl salicylate, vanillyl benzoate, vanillyl phenylacetate, and 9-decenyl benzoate.

(25) (Synthesis Method of Compound Represented by General Formula (1))

(26) The compound represented by general formula (1) of the present invention can be easily synthesized by a known method. The compound represented by general formula (1) can be synthesized, for example, in accordance with the method described in J. Org. Chem. 51.1006 (1986) or J. Org. Chem. 46.5252 (1981).

(27) Out of the compounds represented by general formula (1) of the present invention, a synthesis method of 1-((1R,6S)-2,2,6-trimethylcyclohexyl)-3-hexanyl benzoate represented by the following formula (1a) is shown in the scheme below.

(28) ##STR00008##

(29) As for the synthesis of the compound represented by formula (1a), the compound can be prepared by lithiating a hydroxyl group of Ambestol (compound represented by formula (2)) with butyllithium in a tetrahydrofuran solvent, followed by a reaction with benzoyl chloride. The acylating agent used is preferably benzoyl chloride or benzoic anhydride, etc. The compound represented by formula (1a) obtained as above can be isolated and purified, for example, by an operation usually employed, such as extraction, distillation, recrystallization and various chromatographies.

(30) [Method for Releasing Fragrance Alcohol, Phenol or Phenol Derivative]

(31) A fragrance alcohol, a phenol or a phenol derivative, which are an aromatic component, can be released by reacting the compound represented by general formula (1) with a hydrolase or microorganism.

(32) The method for reacting the compound represented by general formula (1) with a hydrolase includes, for example, a method of mixing the compound represented by general formula (1) with a hydrolase-containing aqueous solution.

(33) The content of the hydrolase in the hydrolase-containing aqueous solution is usually from 0.001 to 50 mass %, preferably from 0.01 to 10 mass %.

(34) The mass of the compound represented by general formula (1) used at the time of mixing is usually from 0.001 to 10,000 mg, preferably from 0.01 to 1,000 mg, per 1 g of the hydrolase-containing aqueous solution.

(35) When the compound represented by general formula (1) reacts with a hydrolase, an ester bond in the compound represented by general formula (1) is hydrolyzed, and a fragrance alcohol, a phenol or a phenol derivative is released.

(36) The hydrolase includes lipase, protease, amylase, glycosidase, esterase, etc., and among these, in view of the hydrolysis rate, lipase is preferred.

(37) The lipase is not limited to a particular one and, as long as it is an enzyme that breaks down fat, may be a naturally occurring material or a formulated commercial product.

(38) The method for reacting the compound represented by general formula (1) with a microorganism includes, for example, a method of mixing the compound represented by general formula (1) with a microbial culture.

(39) The method for culturing a microorganism is not particularly limited, and a known method may be used.

(40) The amount of bacteria in the microbial culture is usually from 10.sup.3 to 10.sup.12 cfu/mL, preferably from 106 to 10.sup.10 cfu/mL.

(41) In addition, the mass of the compound represented by general formula (1) used at the time of mixing is usually from 0.01 to 10 mg, preferably from 0.1 to 5 mg, per 1 mL of the microbial culture.

(42) It is considered that when the compound represented by general formula (1) reacts with a microorganism, the compound is ingested inside the microorganism and metabolized, or an ester bond in the compound is hydrolyzed by the action of an enzyme group secreted outside the microorganism, as a result, a fragrance alcohol, a phenol or a phenol derivative is released.

(43) The microorganism includes Staphylococcus bacteria, Corynebacterium bacteria, Propionibacterium bacteria, Pseudomonas bacteria, Bacillus bacteria, Moraxella bacteria, Malassezia fungi, etc.

(44) More specifically, the microorganism includes Staphylococcus aureus, Staphylococcus epidermidis, Corynebacterium xerosis, Propionibacterium acnes, Pseudomonas aeruginosa, Bacillus subtilis, Moraxella osloensis, Malassezia furfur, etc.

(45) [Compounds 001 to 118]

(46) The compound of the present invention is at least one novel compound selected from the group consisting of compounds 001 to 118 shown in Tables 1 to 12 below (hereinafter, sometimes simply referred to as“compound of the present invention”).

(47) TABLE-US-00001 TABLE 1 Compound 001 (E)-hex-2-en-1-yl (E)-3- (4-methoxyphenyl) acrylate Compound 002 0 (E)-hex-2-en-1-yl 4-hydroxybenzoate Compound 003 (E)-hex-3-en-1-yl (E)-3- (4-methoxyphenyl) acrylate Compound 004 (E)-hex-3-en-1-yl 4-hydroxybenzoate Compound 005 (E)-hex-4-en-1-yl 2- hydroxybenzoate Compound 006 (E)-hex-4-en-1-yl 2- phenylacetate Compound 007 (E)-hex-4-en-1-yl cinnamate Compound 008 (E)-hex-4-en-1-yl (E)-3- (4-methoxyphenyl) acrylate Compound 009 (E)-hex-4-en-1-yl 4-hydroxybenzoate Compound 010 3,7-dimethylocta- 1,6-dien-3-yl (E)-3- (4-methoxyphenyl) acrylate Compound 011 3,7-dimethylocta- 1,6-dien-3- yl 4-hydroxybenzoate

(48) TABLE-US-00002 TABLE 2 Compound 012 0 3,7-dimethyloct- 6-en-1-yl (E)-3-(4- methoxyphenyl) acrylate Compound 013 4-allyl-2-methoxyphenyl 4-hydroxybenzoate Compound 014 (E)-2-methoxy-4- (prop-1-en-1- yl)phenyl 2- hydroxybenzoate Compound 015 (E)-2-methoxy-4- (prop-1-en-1-yl) phenyl 4- methoxybenzoate Compound 016 2-methoxy-4-((E)- prop-1-en-1-yl) phenyl (E)-3-(4- methoxyphenyl) acrylate Compound 017 (E)-2-methoxy-4- (prop-1-en-1-yl) phenyl 4- hydroxybenzoate Compound 018 2,6-dimethyloct-7- en-2-yl benzoate Compound 019 2,6-dimethyloct-7-en-2- yl 2-hydroxybenzoate Compound 020 2,6-dimethyloct-7-en- 2-yl 2-phenylacetate

(49) TABLE-US-00003 TABLE 3 Compound 021 2,6-dimethyloct- 7-en-2-yl cinnamate Compound 022 0 2,6-dimethyloct- 7-en-2-yl 4-methoxybenzoate Compound 023 2,6-dimethyloct- 7-en-2-yl (E)-3-(4- methoxyphenyl) acrylate Compound 024 2,6-dimethyloct-7-en- 2-yl 4-hydroxybenzoate Compound 025 3,7-dimethyloctan- 3-yl benzoate Compound 026 3,7-dimethyloctan- 3-yl 2-hydroxybenzoate Compound 027 3,7-dimethyloctan- 3-yl 2-phenylacetate Compound 028 3,7-dimethyloctan- 3-yl cinnamate Compound 029 3,7-dimethyloctan- 3-yl 4-methoxybenzoate Compound 030 3,7-dimethyloctan-3-yl (E)-3-(4- methoxyphenyl)acrylate Compound 031 3,7-dimethyloctan- 3-yl 4-hydroxybenzoate

(50) TABLE-US-00004 TABLE 4 Compound 032 0 (Z)-3,7-dimethylnona- 1,6-dien-3-yl benzoate Compound 033 (Z)-3,7-dimethylnona- 1,6-dien-3-yl 2- hydroxybenzoate Compound 034 (Z)-3,7-dimethylnona- 1,6-dien-3-yl 2- phenylacetate Compound 035 (Z)-3,7-dimethylnona- 1,6-dien-3-yl cinnamate Compound 036 ((Z)-3,7-dimethylnona- 1,6-dien-3-yl 4- methoxybenzoate Compound 037 (Z)-3,7-dimethylnona- 1,6-dien-3-yl (E)-3-(4- methoxyphenyl) acrylate Compound 038 (Z)-3,7-dimethylnona- 1,6-dien-3-yl 4- hydroxybenzoate Compound 039 2-(4-methylcyclohex- 3-en-1-yl) propan-2-yl 4- methoxybenzoate Compound 040 2-(4-methylcyclohex- 3-en-1-yl) propan-2-yl (E)-3- (4-methoxyphenyl) acrylate Compound 041 1-methyl-4- (prop-1-en-2-yl) cyclohexyl 2- hydroxybenzoate Compound 042 0 1-methyl-4- (prop-1-en-2-yl) cyclohexyl 2- phenylacetate

(51) TABLE-US-00005 TABLE 5 Compound 043 1-methyl-4-(prop-1- en-2-yl)cyclohexyl cinnamate Compound 044 1-methyl-4- (prop-1-en-2-y) cyclohexyl 4- methoxybenzoate Compound 045 1-methyl-4-(prop- 1-en-2-yl)cyclohexyl (E)-3-(4- methoxyphenyl) acrylate Compound 046 1-methyl-4- (prop-1-en-2-yl) cyclohexyl 4- hydroxybenzoate Compound 047 1-methyl-4- (propan-2-ylidene) cyclohexyl 2- hydroxybenzoate Compound 048 1-methyl-4- (propan-2-ylidene) cyclohexyl 2- phenylacetate Compound 049 1-methyl-4- (propan-2-ylidene) cyclohexyl cinnamate Compound 050 1-methyl-4- (propan-2-ylidene) cyclohexyl 4- methoxybenzoate Compound 051 1-methyl-4- (propan-2-ylidene) cyclohexyl (E)-3-(4- methoxyphenyl) acrylate Compound 052 0 1-methyl-4-(propan- 2-ylidene)cyclohexyl 4- hydroxybenzoate Compound 053 1-isopropyl-4- methylcyclohex- 3-en-1-yl 2- hydroxybenzoate

(52) TABLE-US-00006 TABLE 6 Compound 054 1-isopropyl-4- methylcyclohex- 3-en-1-yl 2- phenylacetate Compound 055 1-isopropyl-4- methylcyclohex- 3-en-1-yl (E)-3-(4- methoxyphenyl) acrylate Compound 056 1-isopropyl-4- methylcyclohex- 3-en-1-yl 4- hydroxybenzoate Compound 057 2,6-dimethylheptan- 2-yl benzoate Compound 058 2,6-dimethylheptan-2-yl 2-hydroxybenzoate Compound 059 2,6-dimethylheptan-2-yl 2-phenylacetate Compound 060 2,6-dimethylheptan- 2-yl cinnamate Compound 061 2,6-dimethylheptan-2-yl 4-methoxybenzoate Compound 062 0 2,6-dimethylheptan- 2-yl (E)-3-(4- methoxyphenyl) acrylate Compound 063 2,6-dimethylheptan-2-yl 4-hydroxybenzoate Compound 064 2,6-dimethyl- 8-oxooctan- 2-yl benzoate

(53) TABLE-US-00007 TABLE 7 Compound 065 2,6-dimethyl-8- oxooctan-2-yl 2-hydroxybenzoate Compound 066 (2,6-dimethyl- 8-oxooctan-2-yl 2-phenylacetate Compound 067 2,6-dimethyl-8-oxooctan-2- yl cinnamate Compound 068 2,6-dimethyl-8-oxooctan- 2-yl 4-methoxybenzoate Compound 069 2,6-dimethyl-8-oxooctan- 2-yl (E)-3-(4- methoxyphenyl)acrylate Compound 070 2,6-dimethyl- 8-oxooctan-2-yl 4-hydroxybenzoate Compound 071 4-(tert-butyl) cyclohexyl cinnamate Compound 072 0 4-methoxyphenyl (E)-3- (4-methoxyphenyl) acrylate Compound 073 2-methyl-1- phenylpropan-2-yl 2-hydroxybenzoate Compound 074 2-methyl-1- phenylpropan-2-yl cinnamate Compound 075 2-methyl-1- phenylpropan-2-yl 4-methoxybenzoate

(54) TABLE-US-00008 TABLE 8 Compound 076 2-methyl-1- phenylpropan- 2-yl (E)-3-(4- methoxyphenyl) acrylate Compound 077 2-methyl-1- phenylpropan-2-yl 4-hydroxybenzoate Compound 078 3-methyl- 5-phenylpentyl 2-hydroxybenzoate Compound 079 3-methyl-5- phenylpentyl 2-phenylacetate Compound 080 3-methyl-5- phenylpentyl cinnamate Compound 081 3-methyl-5-phenyl- pentyl 4-methoxy- benzoate Compound 082 0 3-methyl-5-phenyl- pentyl (E)-3-(4- methoxyphenyl) acrylate Compound 083 3-methyl-5- phenylpentyl 4-hydroxybenzoate Compound 084 4-formyl-2- methoxyphenyl 2-hydroxybenzoate Compound 085 2-ethoxy-4- formylphenyl 2-hydroxybenzoate

(55) TABLE-US-00009 TABLE 9 Compound 086 2-ethoxy-4- formylphenyl (E)-3-(4- methoxyphenyl) acrylate Compound 087 2-ethoxy-4- formylphenyl 4-hydroxybenzoate Compound 088 4-(3-oxobutyl)phenyl 2-hydroxybenzoate Compound 089 4-(3-oxobutyl)phenyl 2-phenylacetate Compound 090 4-(3-oxobutyl)phenyl cinnamate Compound 091 4-(3-oxobutyl)phenyl 4-methoxybenzoate Compound 092 00 4-(3-oxobutyl)phenyl (E)-3-(4- methoxyphenyl) acrylate Compound 093 01 4-(3-oxobutylphenyl 4-hydroxybenzoate Compound 094 02 1,3,3-trimethylbicyclo [2.2.1]heptan-2-yl 2- hydroxybenzoate

(56) TABLE-US-00010 TABLE 10 Compound 095 03 1,3,3-trimethyl- bicyclo[2.2.1] heptan-2-yl 2- phenylacetate Compound 096 04 1,3,3-trimethyl- bicyclo[2.2.1] heptan-2-yl cinnamate Compound 097 05 1,3,3-trimethyl- bicyclo[2.2.1] heptan-2-yl 4- methoxybenzoate Compound 098 06 1,3,3-trimethyl- bicyclo[2.2.1]heptan- 2-yl (E)-3-(4- methoxyphenyl) acrylate Compound 099 07 1,3,3-trimethyl- bicyclo[2.2.1] heptan-2-yl 4- hydroxybenzoate Compound 100 08 1-((1R,6S)-2,2,6- trimethylcyclohexyl) hexan-3-yl benzoate Compound 101 09 1-((1R,6S)-2,2,6- trimethylcyclohexyl) hexan-3-yl 2- hydroxybenzoate Compound 102 0 1-((1R,6S)-2,2,6- trimethylcyclohexyl) hexan-3-yl 2- phenylacetate Compound 103 1-((1R,6S)-2,2,6- trimethylcyclohexyl) hexan-3-yl cinnamate Compound 104 1-((1R,6S)-2,2,6- trimethylcyclohexyl) hexan-3-yl 4- methoxybenzoate

(57) TABLE-US-00011 TABLE 11 Com- pound 105 1-((1R,6S)-2,2,6- trimethylcyclohexyl) hexan-3-yl (E)- 3-(4-methoxy- phenyl)acrylate Com- pound 106 1-((1R,6S)-2,2,6- trimethylcyclohexyl) hexan-3-yl 4-hydroxybenzoate Com- pound 107 dec-9-en-1-yl 2- hydroxybenzoate Com- pound 108 dec-9-en-1-yl 2- phenylacetate Com- pound 109 dec-9-en-1-yl cinnamate Com- pound 110 dec-9-en-1-yl 4- methoxybenzoate Com- pound 111 dec-9-en-1-yl 4- hydroxybenzoate Com- pound 112 0 (E)-3,7,11-trimethyl- dodeca-6,10-dien- 1-yl benzoate Com- pound 113 (E)-3,7,11-trimethyl- dodeca-6,10-dien-1-yl 2-hydroxybenzoate Com- pound 114 (E)-3,7,11-trimethyl- dodeca-6,10-dien-1-yl 2-phenylacetate

(58) TABLE-US-00012 TABLE 12 Com- pound 115 (E)-3,7,11- trimethyldodeca- 6,10-dien- 1-yl cinnamate Com- pound 116 (E)-3,7,11- trimethyldodeca- 6,10-dien-1-yl 4- methoxy- benzoate Com- pound 117 (E)-3,7,11- trimethyldodeca- 6,10-dien-1-yl (E)-3-(4- methoxyphenyl) acrylate Com- pound 118 (E)-3,7,11- trimethyldodeca- 6,10-dien-1-yl 4- hydroxybenzoate
[Fragrance Composition]

(59) The fragrance composition of the present invention contains the compound of the present invention. The compound of the present invention may be used individually or in combination of two or more kinds and may also be used in appropriate combination with known fragrance components.

(60) Known fragrance components include, for example, natural essential oils such as lemon oil, orange oil, lime oil, bergamot oil, lavandin oil, lavender oil, geranium oil, rose oil and sandalwood oil, hydrocarbons such as α-pinene, β-pinene, limonene, p-cymene and thujone, aliphatic alcohols such as octanol and p-tert-butylcyclohexanol, terpene-based alcohols such as menthol, citronellol and geraniol, aromatic alcohols such as benzyl alcohol and phenylethyl alcohol, aliphatic aldehydes, terpene-based aldehydes, aromatic aldehydes, acetals, chain ketones, cyclic ketones such as damascone, β-ionone and Methylionone, terpene-based ketones such as carvone, menthone, isomenthone and camphor, aromatic ketones such as acetophenone and raspberry ketone, ethers such as dibenzyl ether, oxides such as linalool oxide and rose oxide, musks such as cyclopentadecanolide and cyclohexadecanolide, lactones such as γ-nonalactone, γ-undecalactone and coumarin, aliphatic esters such as acetic acid ester and propionic acid ester, and aromatic esters such as benzoic acid ester and phenylacetic acid ester.

(61) The fragrance composition of the present invention may contain a solvent, for example, ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, pentylene glycol, hexylene glycol, polyethylene glycol, diethyl phthalate, isopropyl myristate, triethyl citrate, benzyl benzoate, glycerin, triacetin, benzyl alcohol, paraffin, isoparaffin, a rosin ester derivative such as Hercolyn, glycol ethers such as 3-methoxy-3-methyl-1-butanol, ethyl carbitol (diethylene glycol monoethyl ether), ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol propyl ether, dipropylene glycol methyl ether acetate and dipropylene glycol butyl ether, a terpene resin such as pinene polymer, silicones such as cyclic silicone, and water, or a fixative.

(62) Furthermore, the fragrance composition of the present invention may further contain, if desired, known components such as higher alcohol, surfactant, antioxidant, ultraviolet absorber, chelating agent, solubilizing agent, stabilizing agent, cooling sensation agent, preservative, antimicrobial, bactericide, fungicide, insecticidal component and coloring matter.

(63) The production method of the fragrance composition of the present invention is not limited to particular one, but the fragrance composition of the present invention is obtained, for example, by mixing the above-described components in a usual manner.

(64) The blending amount of the compound of the present invention in the fragrance composition of the present invention is not strictly limited and can be variously changed according to use of the fragrance composition but is preferably from 0.1 to 95.0 mass %, more preferably from 0.5 to 80.0 mass %.

(65) [Aroma Product, Laundry Care Product, Hair Care Product, Cosmetic, or Cleaner]

(66) The compound of the present invention or the fragrance composition of the present invention can be used, individually or in combination of two or more kinds, for a product such as aroma product, laundry care product, hair care product, cosmetic or cleaner.

(67) Furthermore, in the product such as aroma product, laundry care product, hair care product, cosmetic or cleaner, for the purpose of letting the scent emitted from the product itself, the scent during use of the product, and the lingering scent from clothing, hair or skin be more favorable, in addition to the compound of the present invention or the fragrance composition of the present invention, there may be appropriately blended in combination a compounded fragrance; a powder fragrance or scent capsule of a known core-shell type, a matrix type using starch or processed starch, etc.; a scent-impregnated material prepared by impregnating an inorganic porous material such as silica gel or calcium silicate or an organic porous material such as celluloses, with a fragrance; a scent inclusion complex prepared by including a fragrance in α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, hydroxypropylated β-cyclodextrin, highly branched cyclic dextrin, etc.; a known fragrance precursor such as silicic acid ester compound, fatty acid ester compound, acetal compound, hemiacetal compound, Schiff base compound, hemiaminal compound or hydrazone compound, each of which can release a fragrance component; a pro-fragrance; a scent precursor; a pro-perfume, etc.

(68) The aroma product includes, for example, a perfume, eau de cologne, a liquid air freshener, a gel air freshener, a powder air freshener, an impregnated air freshener, a mist air freshener, an aerosol air freshener, a thermal evaporation air freshener, an incense stick, a candle, etc.

(69) The laundry care product include, for example, a mist for clothing, a spray for clothing, a laundry detergent, a fabric softener, etc.

(70) The hair care product includes, for example, a hair shampoo, a hair rinse, a hair conditioner, a hair treatment, a hair tonic, a hair styling agent, a hair dye, a permanent waving agent, a hair growth agent, a hair cologne, etc.

(71) The cosmetic includes, for example, a lotion, a milky lotion, a cosmetic cream, a soap, a liquid soap, a facial cleanser, a sunscreen, an antiperspirant, a bath additive, a lipstick, a foundation, etc.

(72) The cleaner includes, for example, a toilet cleaner, a toilet bowl cleaner, a glass cleaner, a kitchen detergent, a washing machine cleaner, a drain cleaner, a bathroom cleaner, etc.

(73) The compound of the present invention releases a fragrance component by the action of a hydrolase and therefore, is particularly useful when a product having blended therein the compound of the present invention is used in combination with a product having blended therein a hydrolase.

(74) The method for using the products in combination is not limited to particular one but includes a method of using a mutual combination of laundry care products, hair care products, or cosmetics.

(75) The mutual combination of laundry care products includes, for example, (A) a method in which a laundry detergent having blended therein a lipase is used in combination with a mist for clothing, a spray for clothing, a fabric softener, etc. having blended therein the compound of the present invention, and (B) a method in which a laundry detergent having blended therein the compound of the present invention is used in combination with a mist for clothing, a spray for clothing, a fabric softener, etc. having blended therein a lipase.

(76) The mutual combination of hair care products includes, for example, (A) a method in which a shampoo having blended therein a lipase is used in combination with a hair rinse, a hair conditioner, a hair treatment, a hair styling agent, a hair growth agent, a hair cologne, etc. having blended therein the compound of the present invention, and (B) a method in which a shampoo having blended therein the compound of the present invention is used in combination with a hair rinse, a hair conditioner, a hair treatment, a hair styling agent, a hair growth agent, a hair cologne, etc., having blended therein a lipase.

(77) The blending amount of the compound of the present invention in each product is not strictly limited and can be variously changed according to use thereof but is preferably from 0.0001 to 10 mass %, more preferably from 0.001 to 5 mass %.

(78) [Deodorant]

(79) The compound of the present invention or the fragrance composition of the present invention can be used, individually or in combination of two or more kinds, for a deodorant.

(80) The deodorant of the present invention can be used after making a formulating by optionally blending one kind or two or more kinds of known components selected from a cleaner, an antimicrobial, a fungicide, a deodorant, a natural essential oil, a fragrance, an aroma material, a cooling sensation agent, a warming sensation agent, a rust inhibitor, an antifoaming agent, a pH adjusting agent, water, a solvent, a propellant, a surfactant, an insecticide, a repellent, an insect repellent, a water repellent, a degrading enzyme, an antistatic agent, a coloring matter, an ultraviolet absorber, a preservative, a chelating agent, an antioxidant, a thickener, a gellant, a water-absorbing resin, activated carbon, silica, a porous material, a resin, paper, felt, a higher alcohol, an inorganic salt, etc.

(81) Examples thereof include a cleaner such as alkylamine oxide, alkylamine, alkyl polyglycoside, naphthalenesulfonic acid-formalin condensate, hydrolyzed collagen peptide salt, acylmethyltaurine salt, N-acylamino acid salt, alkyl sulfate, ether carboxylate, ether sulfonate, alkyltrimethylammonium chloride, dialkyltrimethylammonium chloride, alkylamine salt, alkylamidopropyl amino oxide, alkyl betaine, acetic acid betaine, fatty acid soap, etc.; an antimicrobial such as 4-chloro-3,5-xylenol, isopropylmethylphenol, thymol, hinokitiol, phenol-based compound, polyphenol, catechin, tannin, natural products containing these, natural product containing their derivatives, etc., 2-(4′-thiazolyl)-benzimidazole, benzalkonium chloride, benzethonium chloride, cetylpyridinium chloride, triclosan, silver ion, stabilized chlorine dioxide, etc.; a fungicide; a deodorant such as lauryl methacrylate, geranyl crotonate, myristic acid acetophenone, glyoxal, abietic acid, flavonoid, polyphenol, plant extract, amphoteric surfactant, zinc ricinoleate, etc.; a natural essential oil such as lemon oil, orange oil, lime oil, bergamot oil, lavandin oil, lavender oil, geranium oil, rose oil, sandalwood oil, etc.; hydrocarbons such as α-pinene, β-pinene, limonene, p-cymene, thujone, etc.; aliphatic alcohols such as octanol, p-tert-butylcyclohexanol, etc.; terpene-based alcohols such as menthol, citronellol, geraniol, etc.; aromatic alcohols such as benzyl alcohol, phenylethyl alcohol, etc.; a fragrance, for example, aliphatic aldehydes, terpene-based aldehydes, aromatic aldehydes, acetals, chain ketones, cyclic ketones such as damascone, β-ionone, methylionone, etc., terpene-based ketones such as carvone, menthone, isomenthone, camphor, etc., aromatic ketones such as acetophenone, raspberry ketone, etc., ethers such as dibenzyl ether, etc., oxides such as linalool oxide, rose oxide, etc., musks such as cyclopentadecanolide, cyclohexadecanolide, etc., lactones such as γ-nonalactone, γ-undecalactone, coumarin, etc., aliphatic esters such as acetic acid ester, propionic acid ester, etc., and aromatic esters such as benzoic acid ester, phenylacetic acid ester, etc.; a compounded fragrance prepared from the above-described natural essential oil and fragrance; a powder fragrance or scent capsule of a known core-shell type, a matrix type using starch or processed starch, etc.; a scent-impregnated material prepared by impregnating an inorganic porous material such as silica gel, calcium silicate, etc., or an organic porous material such as celluloses, etc., with a fragrance; a scent inclusion complex prepared by including a fragrance in α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, hydroxypropylated β-cyclodextrin, highly branched cyclic dextrin, etc.; an aroma material, for example, a known fragrance precursor, pro-fragrance, scent precursor, pro-perfume, etc., such as silicic acid ester compound, fatty acid ester compound, acetal compound, hemiacetal compound, Schiff base compound, hemiaminal compound, hydrazone compound, etc., which can release a fragrance component; a rust inhibitor such as trisodium citrate, ammonium citrate, sodium nitrite, ammonium benzoate, ammonium nitrite, etc.; an antifoaming agent such as silicone, etc.; a pH adjusting agent such as citric acid, sodium monohydrogenphosphate, sodium dihydrogenphosphate, potassium monohydrogenphosphate, potassium dihydrogenphosphate, etc.; a solvent, for example, water, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, modified alcohol, ethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, pentylene glycol, hexylene glycol, polyethylene glycol, diethyl phthalate, isopropyl myristate, triethyl citrate, benzyl benzoate, glycerin, triacetin, benzyl alcohol, paraffin, isoparaffin, a rosin ester derivative such as Hercolyn, etc., glycol ethers such as 3-methoxy-3-methyl-1-butanol, ethyl carbitol (diethylene glycol monoethyl ether), ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol propyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol butyl ether, etc., a terpene resin such as pinene polymer, etc., and silicones such as cyclic silicone, etc.; a propellant, for example, a liquefied petroleum gas such as propane, n-butane, isobutane, etc., a liquefied gas such as dimethyl ether, fluorocarbon (e.g., CFC (Chloro Fluoro Carbon), HCFC (Hydro Chloro Fluoro Carbon), HFC (Hydro Fluoro Carbon)), etc., and a compressed gas such as nitrogen, carbon dioxide, compressed air, nitrous oxide, etc.; and a surfactant such as polyoxyethylene alkyl ether, polyoxyethylene-polyoxypropylene copolymer, polyoxyethylene hydrogenated castor oil, sorbitan fatty acid ester, etc.

(82) The formulated deodorant of the present invention includes, for example, a deodorizing mist, a deodorizing spray, a liquid deodorant, a gel deodorant, a solid deodorant, a cream deodorant, a sheet-shaped deodorant, a granular deodorant, a beads deodorant, a powder deodorant, a smoke deodorant, a deodorant for toilet odor, a deodorant for urine odor, a deodorant for body odor, a deodorant for sweat odor, a deodorant for foot odor, a deodorant for scalp odor, a deodorant for aging odor, a deodorant for nursing care, a deodorant for raw garbage odor, a fabric deodorizer, a deodorant for damp-dry odor, a deodorant for laundry care, a deodorant for shoe cupboards, a shoe deodorizer, an entrance deodorizer, a room deodorizer, a bedroom deodorizer, a car freshener, a deodorant for drain odor, a deodorant for pets, a deodorant for diapers, a deodorant for closets, a deodorant for air conditioners, etc.

(83) The deodorant of the present invention can be used in a product such as aroma product, laundry care product, hair care product, cosmetic, oral care product, hygiene product, insecticide, insect repellent, dehumidifying agent, cleaner, etc.

(84) The aroma product includes, for example, a liquid air freshener, a gel air freshener, a powder air freshener, an impregnated air freshener, a beads air freshener, a paper air freshener, a permeable film air fresher, a plug-type air freshener, a fan-type air freshener, an ultrasonic air freshener, a water-absorbing polymer air freshener, a mist air freshener, an aerosol air freshener, a thermal evaporation air freshener, an incense stick, a candle, a reed diffuser, etc., to which a deodorizing function is imparted.

(85) The laundry care product includes, for example, a mist for clothing, a spray for clothing, a laundry detergent, a fabric softener, an anti-wrinkle agent, etc., to which a deodorizing function is imparted.

(86) The hair care product includes, for example, a hair shampoo, a hair rinse, a hair conditioner, a hair treatment, a hair tonic, a hair styling agent, a hair dye, a permanent waving agent, a hair growth agent, a hair lotion, a hair spray, etc., to which a deodorizing function is imparted.

(87) The cosmetic includes, for example, a lotion, a milky lotion, a cosmetic cream, a soap, a liquid soap, a facial cleanser, a sunscreen, an antiperspirant, a bath additive, a lipstick, a foundation, etc., to which a deodorizing function is imparted.

(88) The oral care product includes, for example, a toothpaste, a mouthwash, a mouth spray, a mouth freshener, a denture care product, a breath freshening product, etc., to which a deodorizing function is imparted.

(89) The hygiene product includes, for example, a paper diaper, a sanitary product, wet tissue, tissue paper, toilet paper, a mask, etc., to which a deodorizing function is imparted.

(90) The cleaner includes, for example, a toilet cleaner, a toilet bowl cleaner, a glass cleaner, a kitchen detergent, a washing machine cleaner, a drain cleaner, a bathroom cleaner, a denture cleaner, etc., to which a deodorizing function is imparted.

(91) The blending amount of the compound of the present invention in each product is not strictly limited and can be variously changed according to use thereof. The blending amount of the compound of the present invention in each product is preferably from 0.0001 to mass %, more preferably from 0.001 to 5 mass %.

EXAMPLES

(92) The present invention is specifically described below by referring to Examples, but the present invention is not limited thereto. Note that in Examples, unless otherwise specified, “parts” and “%” are on a mass basis.

(Example 1) Synthesis of 3,7-dimethyl-6-octenyl benzoate (citronellyl benzoate)

(93) ##STR00127##

(94) To 31.2 mL of a toluene solution containing 1.56 g (10 mmol) of (S)-citronellol, 2.79 mL (20 mmol) of triethylamine and 12.2 mg (0.1 mmol) of N,N-dimethylaminopyridine, 1.69 g (12 mmol) of benzoic acid chloride was added at 0° C., followed by stirring at room temperature for 24 hours.

(95) After cooling the reaction solution, the reaction was quenched by the addition of water, and the solution was extracted with toluene. The organic layer was washed with water and then concentrated under reduced pressure to obtain a crude product. The resulting crude product was purified by silica gel column chromatography to obtain 2.28 g of the target product.

(Example 2) Synthesis of 1-((1R,6S)-2,2,6-trimethylcyclohexyl)-3-hexanyl Benzoate

(96) ##STR00128##

(97) To 15.8 mL of a tetrahydrofuran solution containing 1.05 g (4.64 mmol) of 1-((1R,6S)-trimethylcyclohexyl)-3-hexanol, 3.23 mL (5.10 mmol) of n-butyllithium was added at 0° C., followed by stirring at 0° C. for 1 hour. Thereafter, 0.72 g (5.10 mmol) of benzoic acid chloride was added, and the resulting mixture was stirred at 0° C. for 1 hour and at room temperature for 5 hours.

(98) After cooling the reaction solution, the reaction was quenched by the addition of an aqueous ammonium chloride solution, and the solution was extracted with toluene. The organic layer was washed with water and then concentrated under reduced pressure to obtain a crude product. The resulting crude product was purified by silica gel column chromatography to obtain 1.50 g of the target product.

(Example 3) Synthesis of 1-((R,6S)-2,2,6-trimethylcyclohexyl)-3-hexanyl Anisate

(99) ##STR00129##

(100) To 15.8 mL of a tetrahydrofuran solution containing 1.05 g (4.64 mmol) of 1-((1R,6S)-trimethylcyclohexyl)-3-hexanol, 3.23 mL (5.10 mmol) of n-butyllithium was added at 0° C., followed by stirring at 0° C. for 1 hour. Thereafter, 0.87 g (5.10 mmol) of p-methoxybenzoic acid chloride was added, and the resulting mixture was stirred at 0° C. for 1 hour and at room temperature for 5 hours.

(101) After cooling the reaction solution, the reaction was quenched by the addition of an aqueous ammonium chloride solution, and the solution was extracted with toluene. The organic layer was washed with water and then concentrated under reduced pressure to obtain a crude product. The resulting crude product was purified by silica gel column chromatography to obtain 1.60 g of the target product.

(Example 4) Synthesis of 1-((1R,6S)-2,2,6-trimethylcyclohexyl)-3-hexanyl Toluate

(102) ##STR00130##

(103) To 15.8 mL of a tetrahydrofuran solution containing 1.05 g (4.64 mmol) of 1-((1R,6S)-trimethylcyclohexyl)-3-hexanol, 3.23 mL (5.10 mmol) of n-butyllithium was added at 0° C., followed by stirring at 0° C. for 1 hour. Thereafter, 0.79 g (5.10 mmol) of p-methylbenzoic acid chloride was added, and the resulting mixture was stirred at 0° C. for 0.5 hours and at room temperature for 2 hours.

(104) After cooling the reaction solution, the reaction was quenched by the addition of an aqueous ammonium chloride solution, and the solution was extracted with toluene. The organic layer was washed with water and then concentrated under reduced pressure to obtain a crude product. The resulting crude product was purified by silica gel column chromatography to obtain 1.50 g of the target product.

(Example 5) Synthesis of 1-((R,6S)-2,2,6-trimethylcyclohexyl)-3-hexanyl Cinnamate

(105) ##STR00131##

(106) To 15.8 mL of a tetrahydrofuran solution containing 1.05 g (4.64 mmol) of 1-((1R,6S)-trimethylcyclohexyl)-3-hexanol, 3.23 mL (5.10 mmol) of n-butyllithium was added at 0° C., followed by stirring at 0° C. for 1 hour. Thereafter, 0.85 g (5.10 mmol) of cinnamoyl chloride was added, and the resulting mixture was stirred at 0° C. for 1 hour and at room temperature for 5 hours.

(107) After cooling the reaction solution, the reaction was quenched by the addition of an aqueous ammonium chloride solution, and the solution was extracted with toluene. The organic layer was washed with water and then concentrated under reduced pressure to obtain a crude product. The resulting crude product was purified by silica gel column chromatography to obtain 1.57 g of the target product.

(Example 6) Synthesis of (1R,2S,5R)-isopropyl-5-methylcyclohexyl benzoate (menthyl benzoate)

(108) ##STR00132##

(109) To 23.4 mL of a tetrahydrofuran solution containing 1.56 g (10 mmol) of (1R,2S,5R)-2-isopropyl-5-methylcyclohexanol, 6.65 mL (10.5 mmol) of n-butyllithium was added at 0° C., followed by stirring at 0° C. for 1 hour. Thereafter, 1.48 g (10.5 mmol) of benzoic acid chloride was added, and the resulting mixture was stirred at 0° C. for 1.0 hours and at room temperature for 4 hours.

(110) After cooling the reaction solution, the reaction was quenched by the addition of an aqueous ammonium chloride solution, and the solution was extracted with toluene. The organic layer was washed with water and then concentrated under reduced pressure to obtain a crude product. The resulting crude product was purified by silica gel column chromatography to obtain 2.55 g of the target product.

(Example 7) Synthesis of (S,E)-3,7,11-trimethyl-6,10-dodecadienyl Benzoate

(111) ##STR00133##

(112) To 22.4 mL of a toluene solution containing 1.12 g (5 mmol) of (S)-dihydrofarnesol, 1.39 mL (10 mmol) of triethylamine and 12.2 mg (0.1 mmol) of N,N-dimethylaminopyridine, 0.84 g (6 mmol) of benzoic acid chloride was added at 0° C., followed by stirring at room temperature for 24 hours.

(113) After cooling the reaction solution, the reaction was quenched by the addition of water, and the solution was extracted with toluene. The organic layer was washed with water and then concentrated under reduced pressure to obtain a crude product. The resulting crude product was purified by silica gel column chromatography to obtain 1.58 g of the target product.

(Example 8) Synthesis of (S,E)-3,7,11-trimethyl-6,10-dodecadienyl Anisate

(114) ##STR00134##

(115) To 22.4 mL of a toluene solution containing 1.12 g (5 mmol) of (S)-dihydrofarnesol, 1.39 mL (10 mmol) of triethylamine and 12.2 mg (0.1 mmol) of N,N-dimethylaminopyridine, 1.02 g (6 mmol) of p-methoxybenzoic acid chloride was added at 0° C., followed by stirring at room temperature for 24 hours.

(116) After cooling the reaction solution, the reaction was quenched by the addition of water, and the solution was extracted with toluene. The organic layer was washed with water and then concentrated under reduced pressure to obtain a crude product. The resulting crude product was purified by silica gel column chromatography to obtain 1.58 g of the target product.

(Example 9) Synthesis of (S,E)-3,7,11-trimethyl-6,10-dodecadienyl Toluate

(117) ##STR00135##

(118) To 22.4 mL of a toluene solution containing 1.12 g (5 mmol) of (S)-dihydrofarnesol, 1.39 mL (10 mmol) of triethylamine and 12.2 mg (0.1 mmol) of N,N-dimethylaminopyridine, 0.93 g (6 mmol) of p-methylbenzoic acid chloride was added at 0° C., followed by stirring at room temperature for 24 hours.

(119) After cooling the reaction solution, the reaction was quenched by the addition of water, and the solution was extracted with toluene. The organic layer was washed with water and then concentrated under reduced pressure to obtain a crude product. The resulting crude product was purified by silica gel column chromatography to obtain 1.59 g of the target product.

(Example 10) Synthesis of (S,E)-3,7,11-trimethyl-6,10-dodecadienyl Cinnamate

(120) ##STR00136##

(121) To 22.4 mL of a toluene solution containing 1.12 g (5 mmol) of (S)-dihydrofarnesol, 1.39 mL (10 mmol) of triethylamine and 12.2 mg (0.1 mmol) of N,N-dimethylaminopyridine, 1.20 g (7.2 mmol) of cinnamoyl chloride was added at 0° C., followed by stirring at room temperature for 24 hours.

(122) After cooling the reaction solution, the reaction was quenched by the addition of water, and the solution was extracted with toluene. The organic layer was washed with water and then concentrated under reduced pressure to obtain a crude product. The resulting crude product was purified by silica gel column chromatography to obtain 1.55 g of the target product.

(Example 11) Synthesis of (Z)-3-hexenyl Benzoate

(123) ##STR00137##

(124) To 30 mL of a toluene solution containing 1.00 g (10 mmol) of (Z)-3-hexenol, 2.79 mL (20 mmol) of triethylamine and 12.2 mg (0.1 mmol) of N,N-dimethylaminopyridine, 1.69 g (12 mmol) of benzoic acid chloride was added at 0° C., followed by stirring at room temperature for 24 hours.

(125) After cooling the reaction solution, the reaction was quenched by the addition of water, and the solution was extracted with toluene. The organic layer was washed with water and then concentrated under reduced pressure to obtain a crude product. The resulting crude product was purified by silica gel column chromatography to obtain 1.90 g of the target product.

(Example 12) Synthesis of 4-allyl-2-methoxyphenyl benzoate

(126) ##STR00138##

(127) To 41.0 mL of a toluene solution containing 1.64 g (10 mmol) of eugenol, 2.09 mL (15 mmol) of triethylamine and 12.2 mg (0.1 mmol) of N,N-dimethylaminopyridine, 1.69 g (12 mmol) of benzoic acid chloride was added at 0° C., followed by stirring at room temperature for 24 hours.

(128) After cooling the reaction solution, the reaction was quenched by the addition of water, and the solution was extracted with toluene. The organic layer was washed with water and then concentrated under reduced pressure to obtain a crude product. The resulting crude product was purified by silica gel column chromatography to obtain 2.67 g of the target product.

(Example 13) Synthesis of 4-formyl-2-methoxyphenyl Benzoate

(129) ##STR00139##

(130) To 38.0 mL of a toluene solution containing 1.52 g (10 mmol) of vanillin, 2.09 mL (15 mmol) of triethylamine and 12.2 mg (0.1 mmol) of N,N-dimethylaminopyridine, 1.69 g (12 mmol) of benzoic acid chloride was added at 0° C., followed by stirring at room temperature for 24 hours.

(131) After cooling the reaction solution, the reaction was quenched by the addition of water, and the solution was extracted with toluene. The organic layer was washed with water and then concentrated under reduced pressure to obtain a crude product. The resulting crude product was purified by silica gel column chromatography to obtain 2.54 g of the target product.

(Example 14) Synthesis of 9-decenyl Benzoate

(132) ##STR00140##

(133) To 31.2 mL of a toluene solution containing 1.56 g (10 mmol) of 9-decen-1-ol, 2.79 mL (20 mmol) of triethylamine and 12.2 mg (0.1 mmol) of N,N-dimethylaminopyridine, 1.69 g (12 mmol) of benzoic acid chloride was added at 0° C., followed by stirring at room temperature for 5 hours.

(134) After cooling the reaction solution, the reaction was quenched by the addition of water, and the solution was extracted with toluene. The organic layer was washed with water and then concentrated under reduced pressure to obtain a crude product. The resulting crude product was purified by silica gel column chromatography to obtain 2.54 g of the target product.

(Examples 15 to 33) Lipase-Induced Scent Emission Test

(135) 10 mg of a fragrance precursor and 1 g of an aqueous 1% lipase preparation solution were put in a vial bottle and mixed and after hermetically sealing the bottle, the mixture was subjected to GC/MS analysis of the head space component to obtain a peak area of the scent-emitting compound. As a control, water was used in place of the aqueous 1% lipase preparation solution, and a peak area of the control was obtained by the same method. The scent emission amount was determined from the difference between the obtained peak area of the scent-emitting compound and the peak area of the control. The results are shown in Tables 13 and 14.

(136) (GC/MS Measurement Conditions)

(137) Measurement instrument: 7890GC/5975M (manufactured by Agilent Technologies) Column: BC-WAX50 m×0.25 mm I.D. Temperature rise: 70° C. to 220° C., 4° C./min Split ratio: 60:1

(138) TABLE-US-00013 TABLE 13 Scent emission by the action of lipase preparation AY “Amano” 30SD (produced by Amano Enzyme Inc.) Scent Emission Scent-Emitting Example Fragrance Precursor Amount Compound 15 compound of Example 11 49,663,459 (Z)-3-hexenol 16 (Z)-3-hexenyl salicylate 16,933,990 (Z)-3-hexenol 17 geranyl benzoate 78,461,812 geraniol 18 phenylethyl benzoate 96,460,830 phenylethyl alcohol 19 compound of Example 6 82,023,336 menthol 20 phenylethyl phenylacetate 50,855,859 phenylethyl alcohol 21 geranyl phenylacetate 54,842,763 geraniol 22 rosinyl phenylacetate 56,492,946 rosinol 23 cinnamyl cinnamate 24,711,289 cinnamic alcohol 24 phenylethyl cinnamate 22,892,002 phenylethyl alcohol 25 compound of Example 7 88,986,381 dihydrofarnesol 26 compound of Example 8 23,338,647 dihydrofarnesol 27 compound of Example 9 19,259,897 dihydrofarnesol 28 compound of Example 3 40,373,157 1-((1R,6S)- trimethylcyclohexyl)- 3-hexanol

(139) TABLE-US-00014 TABLE 14 Scent emission by the action of lipase preparation Lipex 100 L (produced by Novozymes) Scent Emission Scent-Emitting Example Fragrance Precursor Amount Compound 29 compound of Example 1 28,098,876 citronellol 30 compound of Example 12 164,744,420 eugenol 31 compound of Example 13 47,188,750 vanillin 32 compound of Example 10 19,967,420 dihydrofarnesol 33 compound of Example 3 40,430,750 1-((1R,6S)- trimethylcyclohexyl)- 3-hexanol

(Examples 34 and 35, Comparative Example 1) Test for Confirming Scent Emission from Hair when Using Shampoo

(140) Shampoos were prepared according to the formulation shown in Table 15. A hair bundle of 10 cm in length was cleaned using the prepared shampoo and rinsed with tap water. After drying at room temperature for 15 hours, about 0.3 g of an aqueous 1%/lipase preparation solution was sprayed onto the hair bundle, and the scent on the hair bundle was smelled to examine the presence or absence of scent emission from hair. As the lipase preparation, AY “Amano” 30SD was used.

(141) TABLE-US-00015 TABLE 15 Formulation of shampoo (mass %) Example Example Comparative Raw Material 34 35 Example 1 Sodium polyoxyethylene lauryl 14 14 14 ether sulfate Laurylsulfuric acid amidopropyl betaine 4 4 4 Coconut fatty acid diethanolamide 3 3 3 Cationized cellulose 0.5 0.5 0.5 Ethylene glycol distearate 1 1 1 Paraoxybenzoic acid ester 0.2 0.2 0.2 Geranyl benzoate 0.3 0 0 Compound of Example 12 0 0.3 0 Geraniol 0 0 0.3 Deionized water 77 77 77 Total (mass %) 100 100 100

(142) It could be confirmed that the geraniol odor is emitted by reacting the hair after drying obtained using the shampoo prepared in Example 34 with lipase.

(143) It could be confirmed that the eugenol odor is emitted by reacting the hair after drying obtained using the shampoo prepared in Example 35 with lipase.

(144) The hair after drying obtained using the shampoo prepared in Comparative Example 1 was reacted with lipase, but an odor could not be confirmed.

(Examples 36 and 37, Comparative Example 2) Test for Confirming Scent Emission from Hair when Using Hair Conditioner

(145) Hair conditioners were prepared according to the formulation shown in Table 16. A hair bundle of 10 cm in length was treated with the hair conditioner prepared and rinsed with tap water. After drying at room temperature for 15 hours, about 0.3 g of an aqueous 1% lipase preparation solution was sprayed onto the hair bundle, and the odor on the hair bundle was smelled to examine the presence or absence of scent emission from hair. As the lipase preparation, AY “Amano” 30SD was used.

(146) TABLE-US-00016 TABLE 16 Formulation of hair conditioner (mass %) Example Example Comparative Raw Material 36 37 Example 2 Stearyltrimethylammonium chloride 0.5 0.5 0.5 Distearyldimethylammonium chloride 1.5 1.5 1.5 Cetanol 4.5 4.5 4.5 Amino-modified silicone 0.5 0.5 0.5 Glycerin 5 5 5 Paraoxybenzoic acid ester 0.2 0.2 0.2 Compound of Example 6 0.3 0 0 Compound of Example 1 0 0.3 0 Citronellol 0 0 0.3 Deionized water 87.5 87.5 87.5 Total (mass %) 100 100 100

(147) It could be confirmed that the menthol odor is emitted by reacting the hair after drying obtained using the hair conditioner prepared in Example 36 with lipase.

(148) It could be confirmed that the citronellol odor is emitted by reacting the hair after drying obtained using the hair conditioner prepared in Example 37 with lipase.

(149) The hair after drying obtained using the hair conditioner prepared in Comparative Example 2 was reacted with lipase, but an odor could not be confirmed.

(Examples 38 to 40, Comparative Example 3) Test for Confirming Scent Emission from Towel when Using Liquid Detergent

(150) Liquid detergents were prepared according to the formulation shown in Table 17. A cotton towel was cleaned with the liquid detergent prepared and rinsed with tap water. After drying at room temperature for 15 hours, about 0.3 g of an aqueous 1% lipase preparation solution was sprayed onto the towel, and the odor on the towel was smelled to examine the presence or absence of scent emission from towel. As the lipase preparation, AY “Amano” 30SD was used.

(151) TABLE-US-00017 TABLE 17 Formulation of liquid detergent (mass %) Example Example Example Comparative Raw Material 38 39 40 Example 3 Polyoxyethylene alkyl ether 40 40 40 40 Linear alkylbenzenesulfonate 18 18 18 18 Butyl carbitol 10 10 10 10 Propylene glycol 3 3 3 3 Monoethanolamine 3 3 3 3 Phenylethyl salicylate 0.5 0 0 0 Compound of Example 1 0 0.5 0 0 Compound of Example 12 0 0 0.5 0 Phenylethyl alcohol 0 0 0 0.5 Deionized water 25.5 25.5 25.5 25.5 Total (mass %) 100 100 100 100

(152) It could be confirmed that the phenylethyl alcohol odor is emitted by reacting the towel after drying obtained using the liquid detergent prepared in Example 38 with lipase.

(153) It could be confirmed that the citronellol odor is emitted by reacting the towel after drying obtained using the liquid detergent prepared in Example 39 with lipase.

(154) It could be confirmed that the eugenol odor is emitted by reacting the towel after drying obtained using the liquid detergent prepared in Example 40 with lipase.

(155) The towel after drying obtained using the liquid detergent prepared in Comparative Example 3 was reacted with lipase, but an odor could not be confirmed.

(Examples 41 to 43, Comparative Example 4) Test for Confirming Scent Emission from Towel when Using Softener

(156) Softeners were prepared according to the formulation shown in Table 18. A cotton towel was treated with the softener prepared and rinsed with tap water. After drying at room temperature for 15 hours, about 0.3 g of an aqueous 1% lipase preparation solution was sprayed onto the towel, and the odor on the towel was smelled to examine the presence or absence of scent emission from towel. As the lipase preparation, AY “Amano” 30SD was used.

(157) TABLE-US-00018 TABLE 18 Formulation of softener (mass %) Example Example Example Comparative Raw Material 41 42 43 Example 4 Tri(oxyethylene)methyl- 18 18 18 18 ammonium methylsulfate fatty acid ester Polyoxyethylene(23) lauryl 3 3 3 3 ether Propylene glycol 3 3 3 3 Calcium chloride 0.1 0.1 0.1 0.1 Phenylethyl benzoate 0.5 0 0 0 Geranyl phenylacetate 0 0.5 0 0 Compound of Example 7 0 0 0.5 0 Geraniol 0 0 0 0.5 Deionized water 75.4 75.4 75.4 75.4 Total (mass %) 100 100 100 100

(158) It could be confirmed that the phenylethyl alcohol odor is emitted by reacting the towel after drying obtained using the softener prepared in Example 41 with lipase.

(159) It could be confirmed that the geraniol odor is emitted by reacting the towel after drying obtained using the softener prepared in Example 42 with lipase.

(160) It could be confirmed that the dihydrofamesol odor is emitted by reacting the towel after drying obtained using the softener prepared in Example 43 with lipase.

(161) The towel after drying obtained using the softener prepared in Comparative Example 4 was reacted with lipase, but an odor could not be confirmed.

(Examples 44 and 45, Comparative Example 5) Fragrance Composition

(162) Fragrance compositions were prepared according to the formulation shown in Table 19.

(163) TABLE-US-00019 TABLE 19 Formulation of fragrance composition (parts by mass) Example Example Comparative Raw Material 44 45 Example 5 Undecylene aldehyde 5 5 5 Allylamyl glycolate 2 2 2 Allyl enanthate 5 5 5 Benzyl acetate 10 10 10 Borneol 5 5 5 Cinnamic alcohol 8 8 8 Citronellol 50 50 50 Coumarin 3 3 3 Tricyclodecenyl acetate 60 60 60 α-Damascone 1 1 1 Dihydromyrcenol 60 60 60 Diphenyl oxide 3 3 3 Eucalyptus oil 1 1 1 Geraniol 30 30 30 Methyl dihydrojasmonate 40 40 40 Hexyl cinnamic aldehyde 40 40 40 Lime oil 25 25 25 Lemon oil 30 30 30 Linalol 80 80 80 Linalyl acetate 40 40 40 MUSK T (produced by Takasago 100 100 100 International Corporation) γ-Methylionone 20 20 20 Methyl nonyl ketone 2 2 2 Nerol 20 20 20 ORBITONE (produced by Takasago 40 40 40 International Corporation) 4-tert-Butylcyclohexanol 20 20 20 p-tert-Butylcyclohexyl acetate 100 100 100 Geranyl phenylacetate 200 0 0 Compound of Example 3 0 200 0 Dipropylene glycol 0 0 200 Total (parts by mass) 1000 1000 1000 MUSK T (registered trademark) ORBITONE (registered trademark)

(Examples 46 to 51, Comparative Examples 6 to 12) Liquid Detergent/Softener Combination Use Test

(164) Liquid detergents with or without lipase were prepared according to the formulation shown in Table 20. In addition, softeners were prepared according to the formulation shown in Table 21.

(165) TABLE-US-00020 TABLE 20 Formulation of liquid detergent (mass %) Raw Material With Lipase Without Lipase Polyoxyethylene alkyl ether 40 40 Linear alkylbenzenesulfonate 18 18 Butyl carbitol 10 10 Propylene glycol 3 3 Monoethanolamine 3 3 Lipase preparation/Lipex 100 L 1 — Deionized water 25 26 Total (mass %) 100 100 Lipex 100 L: produced by Novozymes

(166) TABLE-US-00021 TABLE 21 Formulation of softener (mass %) Example Example Comparative Raw Material 46 47 Example 6 Fragrance composition of Example 44 0.5 0 0 Fragrance composition of Example 45 0 0.5 0 Fragrance composition of Comparative 0 0 0.5 Example 5 Tri(oxyethylene)methylammonium 18 18 18 methylsulfate fatty acid ester Polyoxyethylene(23) lauryl ether 3 3 3 Propylene glycol 3 3 3 Calcium chloride 0.05 0.05 0.05 Citric acid 0.01 0.01 0.01 Sodium citrate 0.1 0.1 0.1 Deionized water 75.34 75.34 75.34 Total (mass %) 100 100 100

(167) A cotton towel was cleaned with the liquid detergent obtained above, and the cotton towel after cleaning was dehydrated and then treated with the softener obtained above. After dehydration, the towel was dried overnight. The scent intensity and fresh feeling of the cotton towel during drying and after drying were evaluated by ten expert panelists according to the following evaluation criteria. The evaluation score was determined by averaging the evaluation values of the ten expert panelists. The results are shown in Tables 22 and 23.

(168) (Evaluation Criteria of Scent Intensity)

(169) 0: Odorless 1: Barely perceivable odor 2: Odor can be identified as what odor but is weak 3: Easily perceivable odor 4: Strong odor 5: Intense odor
(Evaluation Criteria of Fresh Feeling) 0: No fresh feeling is sensed. 1: Fresh feeling is faintly sensed. 2: Fresh feeling is slightly sensed. 3: Fresh feeling is sensed. 4: Fresh feeling is fairly sensed.

(170) TABLE-US-00022 TABLE 22 Results of scent intensity Example Comparative Example Comparative Comparative 48 Example 7 49 Example 8 Example 9 Liquid with without with without with lipase detergent lipase lipase lipase lipase Softener Example Example Example Example Comparative 46 46 47 47 Example 6 During 3.2 2.6 3.3 2.5 2.5 drying After 2.5 1.2 2.8 1.2 1.0 drying

(171) TABLE-US-00023 TABLE 23 Results of fresh feeling Example Comparative Example Comparative Comparative 50 Example 10 51 Example 11 Example 12 Liquid with without with without with lipase detergent lipase lipase lipase lipase Softener Example Example Example Example Comparative 46 46 47 47 Example 6 During 3.6 2.4 3.7 2.6 2.4 drying After 2.8 0.5 3.3 0.7 0.5 drying

(172) It could be confirmed from the results in Tables 22 and 23 that when a softener using a compounded fragrance having blended therein a compound represented by general formula (1) of the present invention is used in combination with a liquid detergent having blended therein lipase, scent emission occurs and the scent intensity and the fresh feeling of lingering scent are enhanced.

(173) It could be confirmed from the results in Tables 22 and 23 that the fragrance precursor of the present invention releases a scent-emitting compound having a hydroxy group by the action of lipase.

(Examples 52 to 68) Scent Emission Test by Microorganism

(174) (Microorganism Culturing Method)

(175) Culture of Staphylococcus aureus strain NBRC12732, Corynebacterium xerosis strain JCM1324, Pseudomonas aeruginosa strain NBRC13275, and Moraxella osloensis strain ATCC19976:

(176) After inoculating each of bacteria in Muller-Hinton liquid medium, shaking culture was performed at 30° C. for 20 hours, and 3 mL of the resulting preculture solution was transferred to a vial bottle. 10 mg of each of the fragrance precursors was mixed therewith and after hermetical sealing, shaking culture was further performed at 30° C. for 20 hours.

(177) Culture of Propionibacterium acnes Strain JCM6473:

(178) After inoculating the bacterium in GAM bouillon liquid medium containing Hemin 0.5 ppm and Menadione 0.5 ppm, static culture was performed at 28° C. for 3 days under anaerobic conditions, and 3 mL of the resulting preculture solution was transferred to a vial bottle. 10 mg of each of the fragrance precursors was mixed therewith and after hermetical sealing, static culture was further performed at 28° C. for 3 days.

(179) Culture of Malassezia furfur Strain NBRC0656:

(180) After inoculating the bacterium in Sabouraud liquid medium containing 0.1% Tween 80, static culture was performed at 28° C. for 3 days under anaerobic conditions, and 3 mL of the resulting preculture solution was transferred to a vial bottle. 10 mg of the fragrance precursor was mixed therewith and after hermetical sealing, static culture was further performed at 28° C. for 3 days.

(181) (Test Method)

(182) A peak area of the scent-emitting compound was obtained by performing GC/MS analysis of the head space component included in the vial bottle containing 3 mL of a microorganism culture solution in which 10 mg of the fragrance precursor was mixed. A microorganism culture solution having not mixed therein the fragrance precursor was used as the control, and a peak area of the control was obtained by the same method. The scent emission amount was determined from the difference between the obtained peak area of the scent-emitting compound and the peak area of the control. The results are shown in Tables 24 to 29.

(183) (GC/MS Measurement Conditions)

(184) Measurement instrument: 7890GC/5975MSD (manufactured by Agilent Technologies) Column: BC-WAX 50 m×0.25 mm I.D. Temperature rise: 70° C. to 220° C., 4° C./min Split ratio: splitless

(185) TABLE-US-00024 TABLE 24 Scent emission amount when mixed with culture solution of Staphylococcus aureus NBRC12732 Scent Emission Scent-Emitting Example Fragrance Precursor Amount Compound 52 geranyl benzoate 839,961,157 geraniol 53 phenylethylene cinnamate 144,750,281 phenylethyl alcohol 54 (Z)-3-hexenyl salicylate 14,126,965 (Z)-3-hexenol

(186) It could be confirmed from the results in Table 24 that the fragrance precursor of the present invention releases a scent-emitting compound having a hydroxy group by the action of Staphylococcus aureus NBRC12732.

(187) TABLE-US-00025 TABLE 25 Scent emission amount when mixed with culture solution of Corynebacterium xerosis JCM1324 Scent Emission Scent-Emitting Example Fragrance Precursor Amount Compound 55 geranyl phenylacetate 39,033,900 geraniol

(188) It could be confirmed from the results in Table 25 that the fragrance precursor of the present invention releases a scent-emitting compound having a hydroxy group by the action of Corynebacterium xerosis JCM1324.

(189) TABLE-US-00026 TABLE 26 Scent emission amount when mixed with culture solution of Pseudomonas aeruginosa NBRC13275 Scent Emission Scent-Emitting Example Fragrance Precursor Amount Compound 56 geranyl benzoate 117,161,311 geraniol 57 phenylethyl cinnamate 247,508,719 phenylethyl alcohol 58 citronellyl phenylacetate 150,385,642 citronellol

(190) It could be confirmed from the results in Table 26 that the fragrance precursor of the present invention releases a scent-emitting compound having a hydroxy group by the action of Pseudomonas aeruginosa NBRC13275.

(191) TABLE-US-00027 TABLE 27 Scent emission amount when mixed with culture solution of Moraxella osloensis ATCC19976 Scent Emission Scent-Emitting Example Fragrance Precursor Amount Compound 59 citronellyl phenylacetate 500,940,481 citronellol 60 compound of Example 14 86,274,718 9-decenol

(192) It could be confirmed from the results in Table 27 that the fragrance precursor of the present invention releases ascent-emitting compound having a hydroxy group by the action of Moraxella osloensis ATCC 19976.

(193) TABLE-US-00028 TABLE 28 Scent emission amount when mixed with culture solution of Propionibacterium acnes JCM6473 Scent Emission Scent-Emitting Example Fragrance Precursor Amount Compound 61 geranyl benzoate 105,061,217 geraniol 62 phenylethyl cinnamate 112,497,882 phenylethyl alcohol 63 citronellyl phenylacetate 292,401,763 citronellol 64 compound of Example 14 133,440,692 9-decenol

(194) It could be confirmed from the results in Table 28 that the fragrance precursor of the present invention releases ascent-emitting compound having a hydroxy group by the action of Propionibacterium acnes JCM6473.

(195) TABLE-US-00029 TABLE 29 Scent emission amount when mixed with culture solution of Malassezia furfur NBRC0656 Scent Emission Scent-Emitting Example Fragrance Precursor Amount Compound 65 geranyl benzoate 121,633,184 geraniol 66 phenylethyl cinnamate 351,450,490 phenylethyl alcohol 67 citronellyl phenylacetate 369,118,269 citronellol 68 compound of Example 14 304,030,021 9-decenol

(196) It could be confirmed from the results in Table 29 that the fragrance precursor of the present invention releases a scent-emitting compound having a hydroxy group by the action of Malassezia furfur NBRC0656.

(Example 69, Comparative Example 13) Deodorization Test on Odor Emitted from a Microorganism

(197) (Test Method)

(198) A gauze impregnated with Triolein 1 g, Tricaproin 1 g and Androsterone 0.5 g was set as a substrate in a petri dish of 33 mm in diameter ϕ. Furthermore, 1 mL of Staphylococcus aureus test bacterial solution (1×10.sup.9 cfu/mL) previously prepared in 0.9% physiological saline containing 0.2% L-leucine as a substrate was mixed with 3.5 μL of geranyl benzoate, and the resulting mixture was uniformly impregnated into the gauze that was set.

(199) A cover was put on the petri dish and after hermetically sealing it, culture was performed at 37° C. for 20 hours. Sensory evaluation of the degree of pleasantness/unpleasantness of the odor on the gauze after culturing was performed by ten expert panelists according to the following evaluation criteria. The evaluation score was determined by averaging the evaluation values of the ten expert panelists (Example 69).

(200) The degree of pleasantness/unpleasantness of the odor on the gauze after culturing was evaluated in the same manner as in Example 69 except that geranyl benzoate was not mixed (Comparative Example 13). The results are shown in Table 30.

(201) It is known that each of Triolein, Tricaproin, Androsterone and L-leucine emits an offensive odor by the action of a microorganism.

(202) (Evaluation Criteria of Degree of Pleasantness/Unpleasantness)

(203) +4: Extremely pleasant +3: very pleasant +2: pleasant +1: slightly pleasant 0: neither pleasant nor unpleasant −1: slightly unpleasant −2: unpleasant −3: very unpleasant −4: extremely unpleasant

(204) TABLE-US-00030 TABLE 30 Comparative Example 69 Example 13 Degree of pleasantness/unpleasantness 1.2 −3

(205) It was confirmed from the results in Table 30 that as revealed by Comparative Example 13, an offensive odor was emitted along with proliferation of Staphylococcus aureus under the test conditions above. In addition, it could be confirmed that as revealed by Example 69, geranyl benzoate that is a fragrance precursor can alleviate the degree of unpleasantness of the offensive odor caused by Staphylococcus aureus.

Examples 70 to 72

(206) Deodorizing mists were prepared according to the formulation shown in Table 31.

(207) TABLE-US-00031 TABLE 31 Formulation of deodorizing mist (mass %) Example 70 Example 71 Example 72 Citronellyl phenylacetate 1 0 0 Compound of Example 13 0 1 0 Compound of Example 12 0 0 1 Polyoxyethylene(60) 3 3 3 hydrogenated castor oil Deionized water 96 96 96 Total (mass %) 100 100 100

(Examples 73 to 75, Comparative Examples 14 to 16) Deodorization Test on Worn Sock Odor by Deodorizing Mist

(208) (Test Method)

(209) A cleaned chemical-fiber sock for right foot was sprayed with 0.6 g of each of deodorizing mists obtained in Examples 70 to 72 (Examples 73 to 75). Cleaned chemical-fiber socks for left foot, which were not sprayed with the deodorizing mist, were Comparative Examples 14 to 16. Sensory evaluation of the degree of pleasantness/unpleasantness of the odor on the sock after wearing for 15 hours was performed by ten expert panelists according to the evaluation criteria. As for the evaluation criteria, the evaluation criteria of Example 69 were used. The evaluation score was determined by averaging the evaluation values of the ten expert panelists. The results are shown in Table 32.

(210) TABLE-US-00032 TABLE 32 Degree of Deodorizing Foot on which Pleasantness/ Mist Sock Worn Unpleasantness Example 73 Example 70 right foot 2.2 Comparative Example 14 none left foot −2.4 Example 74 Example 71 right foot 2.4 Comparative Example 15 none left foot −2.2 Example 75 Example 72 right foot 2 Comparative Example 16 none left foot −2

(211) The socks of Comparative Examples 14 to 16 not sprayed with the deodorizing mist of the present invention emitted an offensive odor and were felt to be unpleasant, but the odor of the socks of Examples 73 to 75 sprayed with the deodorizing mist of the present invention did not smell unpleasant. It could be confirmed that a deodorizing component is released from citronellyl phenylacetate, the compound of Example 13, and the compound of Example 12, which are fragrance precursors, and the unpleasant sensation is thereby alleviated.

Example 76

(212) A deodorizing spray was prepared according to the formulation shown in Table 33.

(213) TABLE-US-00033 TABLE 33 Formulation of deodorizing spray (mass %) Example 76 Compound of Example 3 0.5 Ethanol 19.5 LPG 80 Total (mass %) 100

(Example 77, Comparative Example 17) Deodorization Test on Sweaty Shirt by Deodorizing Spray

(214) (Test Method)

(215) A right-side underarm portion of a cleaned cotton shirt was sprayed with 1 g of the deodorizing spray obtained in Example 76 (Example 77). In Comparative Example 17, the deodorizing spray was not sprayed onto the left-side underarm portion of the shirt. After wearing the shirts for 24 hours, sensory evaluation of the degree of pleasantness/unpleasantness of the odor in the right-side underarm portion and left-side underarm portion of the shirt was performed by ten expert panelists according to the evaluation criteria. As for the evaluation criteria, the evaluation criteria of Example 69 were used. The evaluation score was determined by averaging the evaluation values of the ten expert panelists. The results are shown in Table 34.

(216) TABLE-US-00034 TABLE 34 Comparative Example 77 Example 17 Degree of pleasantness/unpleasantness 1.8 −3.2

(217) The left-side underarm portion of the shirt not sprayed with the deodorizing spray of the present invention emitted an offensive odor and was felt to be unpleasant, but the odor in the right-side underarm portion of the shirt sprayed with the deodorizing spray of the present invention did not smell unpleasant. It could be confirmed that an aromatic component is released from the compound of Example 3, which is a fragrance precursor, and the unpleasant sensation is thereby alleviated.

(218) While the present invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the present invention. This application is based on Japanese Patent Application (Patent Application No. 2017-184026) filed on Sep. 25, 2017, the contents of which are incorporated herein by way of reference.

INDUSTRIAL APPLICABILITY

(219) The compound represented by general formula (1) can release a fragrance alcohol, a phenol or a phenol derivative, which are an aromatic component or a deodorizing component, by the action of a hydrolase or a microorganism and therefore, is useful.

(220) Blending of the compound represented by general formula (1) of the present invention in a fragrance composition or various products enables development of a product capable of causing a lingering scent with fresh feeling to last on the clothing, hair or skin or responding to a wide range of needs for deodorization, and therefore, the compound has applicability in the fragrance industry.